The adsorption of Zn 2+ ions onto biogenic elemental selenium nanoparticles (BioSeNPs) was investigated. BioSeNPs were produced by reduction of selenite (SeO 3 2− ) in the presence of anaerobic granules from a full scale upflow anaerobic sludge blanket (UASB) reactor treating paper mill wastewater. The BioSeNPs have an iso-electric point at pH 3.8 at 5 mM background electrolyte concentration. X-ray photoelectron spectroscopy showed the presence of a layer of extracellular polymeric substances on the surface of BioSeNPs providing colloidal stability. Batch adsorption experiments showed that the uptake of Zn 2+ ions by BioSeNPs was fast and occurred at a pH as low as 3.9. The maximum adsorption capacity observed was 60 mg of zinc adsorbed per g of BioSeNPs. The Zn 2+ ions adsorption on the BioSeNPs was largely unaffected by the presence of Na + and Mg 2+ , but was impacted by the presence of Ca 2+ and Fe 2+ ions.

Increasing mercury deposition rates in the Northern Hemisphere recorded in natural archives such as peat bogs or lake sediments have been documented in numerous studies. However, data on atmospheric Hg deposition in the Southern Hemisphere dating back to pre-industrial times are rare. Here, we provide a continuous record of atmospheric Hg deposition in the Southern Hemisphere recorded by an ombrotrophic peat bog of the Magellanic Moorlands, Chile (53 ‡S), extending back 3000 yr. Pre-industrial mercury accumulation rates range between 2.5 and 3.9 Wg/m 2 /yr. In the past 100 yr, Hg accumulation rates increased 18-fold from about 3 Wg/m 2 /yr to a maximum of 62.5 Wg/m 2 /yr. If Hg accumulation rates were normalized to peat accumulation rates, maximum rates were 7.9 Wg/m 2 / yr, which is only 2.5 times the pre-industrial rates. Thus, Hg accumulation rates normalized to peat accumulation rates are more comparable to the three-fold net increase in atmospheric Hg concentrations estimated for the same period. We suggest that the increase in Hg accumulation rates in the Magellanic Moorlands within the past 100 yr is at least partly attributed to global dispersion of Hg derived from anthropogenic sources in the Northern Hemisphere. The finding that no increase of atmospheric deposition of Pb could be observed in the bog indicates the extraordinary long-range transport and ubiquitous dispersion of anthropogenic derived gaseous Hg compared to other metals. ß

No abstract

Hematite plays a decisive role in regulating the mobility of contaminants in rocks and soils. The Np(V) reactions at the hematite-water interface were comprehensively investigated by a combined approach of in situ vibrational spectroscopy, X-ray absorption spectroscopy and surface complexation modeling. A variety of sorption parameters such as Np(V) concentration, pH, ionic strength, and the presence of bicarbonate was considered. Time-resolved IR spectroscopic sorption experiments at the iron oxide-water interface evidenced the formation of a single monomer Np(V) inner-sphere sorption complex. EXAFS provided complementary information on bidentate edge-sharing coordination. In the presence of atmospherically derived bicarbonate the formation of the bis-carbonato inner-sphere complex was confirmed supporting previous EXAFS findings.1 The obtained molecular structure allows more reliable surface complexation modeling of recent and future macroscopic data. Such confident modeling is mandatory for evaluating water contamination and for predicting the fate and migration of radioactive contaminants in the subsurface environment as it might occur in the vicinity of a radioactive waste repository or a reprocessing plant.

Mercury (Hg) records in natural archives such as peat bogs are often used to evaluate anthropogenic or climatic influences on atmospheric Hg deposition. In this context, there is an ongoing discussion about natural sources or processes of Hg enrichment in natural archives. In the present study we estimated Hg fluxes from rock weathering, direct atmospheric deposition and from indirect atmospheric deposition in the catchment of a pristine minerogenic fen (GC2) located in the Magellanic Moorlands, southernmost Chile. The Hg record in the bog covers 11 174 cal. (14)C years and shows Hg concentrations of up to 570 [micro sign]g kg(-1) with an average of 268 [micro sign]g kg(-1). Hg was found to be enriched in the peat by a factor of 81 if compared to the mean Hg concentrations in the rocks of the catchment (3.2 [micro sign]g kg(-1)). Hg and also Pb, Fe, and As were found to be enriched predominately in goethite layers indicating high retention of these elements in the bog by iron oxyhydrates. It could also be demonstrated that the high peat decomposition rates in minerogenic bogs can increase the Hg concentrations in the minerogenic peat by a factor of approximately 2 at the same atmospheric Hg deposition rate if compared to ombrotrophic sites. This study has shown that Hg in minerogenic peat can be naturally enriched especially through the retention by autochthonous formed goethite and can be a solely internal process which does not require increased external Hg fluxes.

The aqueous speciation of selenium(iv) was elucidated by a combined approach applying quantum chemical calculations, infrared (IR), Raman, and (77)Se NMR spectroscopy. The dimerization of hydrogen selenite (HSeO3(-)) was confirmed at concentrations above 10 mmol L(-1) by both IR and NMR spectroscopy. Quantum chemical calculations provided the assignment of vibrational bands observed to specific molecular modes of the (HSeO3)2(2-) ion. The results presented will provide a better understanding of the chemistry of aqueous Se(iv) which is of particular interest for processes occurring at mineral/water interfaces.

No abstract

No abstract